AgII‐Mediated Electrocatalytic Ambient CH4 Functionalization Inspired by HSAB Theory

Although most class (b) transition metals have been studied in regard to CH₄ activation, divalent silver (Ag^II ), possibly owing to its reactive nature, is the only class (b) high-valent transition metal center that is not yet reported to exhibit reactivities towards CH₄ activation. We now report that electrochemically generated Ag^II metalloradical readily functionalizes CH₄ into methyl bisulfate (CH₃ OSO₃ H) at ambient conditions in 98 % H₂ SO₄ . Mechanistic investigation experimentally unveils a low activation energy of 13.1 kcal mol^-1 , a high pseudo-first-order rate constant of CH₄ activation up to 2.8×10³ h^-1 at room temperature and a CH₄ pressure of 85 psi, and two competing reaction pathways preferable towards CH₄ activation over solvent oxidation. Reaction kinetic data suggest a Faradaic efficiency exceeding 99 % beyond 180 psi CH₄ at room temperature for potential chemical production from widely distributed natural gas resources with minimal infrastructure reliance.